Process for breaking petroleum emulsions



Patented July 25,1939

. 2,167,347 raocnss FOB. BREAKING PETROLEUM .EMULSIONS Melvin DqGroote, University City, and Bernhard Keiser and Charles M. Blair, Jr., Webster Groves, Mo., assignors, bymesne assignments,

to Petrolite Corporation; Ltd, a corporation of Delaware No Drawing. Application May Serial No. 206,902

'7 Claims (Cl. 196-4) '16 They are obtained from producing wells and from the bottom of oil storage tanks, and are commonly" referred to as cut oilf, roily. oil;

emulsified oil, and bottomsettlings.

The object of our invention is toprovidea novel and inexpensive process for separating emulsions'of the character referred to into their component parts of oil and water or brine.

. Briefly described, our process consists in subjecting a petroleum emulsion'of the water-in-oil "21) type to the action of a treating agent or demul- .sifying agent off-the hereinafter described, thereby causing the emulsion to break down and separate into its componentparts of oil and water or brine, when the emulsion is permitted to remain in a quiescent state after treatment, or is subjected to other equivalent separatory procedures.

The treating agent or demulsifying agent con templated by our process consists of or. comprises 3?) an amine of the kind hereinafter described. Said demulsifying agent may be inv the form of the amine itself, or in the form of the amine base derived by contact withwater; or in the .form of a salt.- The particular amine employed as the 35 rlemulsifying-agent in our process is characterized by the fact that it is derived from a fatty acid orfatty acid ester, suchas a glyceride, in

such a manner that the fatty acid radical or 'resialml, aralkyl, or alicyclic in nature. Said composition'and the method of manufacturingthe.

same will be subsequently described in detail.

acids or their esters; For sake of convenience,

{these materials will bereferred to as fatty acids. The fatty acidsare derived from animal, vege- 56 table, and marine sources and include such mate rials. as palm oil, palm'kernel oil, cocoanut cil',-.;

nitrogen. atom of the amine through a carbon I atom chain, which carbon atom chain is in turn As. previously noted, the amines'employed in the present process are derived from higher fatty oil, etc. For sake of convenience,aeidsoccurring in certain waxes, such as carnaubic acid, cerotic acid, lanopalmic acid, and lanoceric acid, will be considered as fatty acids. v i

. The specific fatty acids present includes among others, oleic acid, stearic acid, linolic acid, linolenic acid, clupanodonic acid, ricinoleic acid, di-

hydroxystearic acid, etc. r

The fatty acids .or suitable derivatives thereof for instance, the'fatty acids themselves or the esters'de'rived from monohydric or dihydrlc alcohols, or the naturally-occurring glycerides, may be reacted with selected tertiary hydroxyamines to give reagents of the kind employed in the present process for resolving oil field emulsions. fNot only.may. the fatty acidsand their esters'be employed, but also suitable derivatives, such' as the form that supplies theacyl radical of the fatty acid.

employed in' the present process are different from various other nitrogenous products, and particularly-various related, amines or .amides, it may be well to indicate briefly certain reactions offatty acids and amines. -In'thecase of primary or secondary amines, the reactions may be indicated by the following:

(A) Salt formation R.COOH+R'NH I-I [I-IHRN.H]OQC.R (B) Amide formation 7 y R.COOH+HIR'NH' RCO.NR'H .(0) The third type of reaction involves ,the

fatty-acid in the form of a salt so as to produce amino fatty acids.

(D) sun another. type of, reactioni involves fatty acids and a,.tertiary alkylolamine or its In order to clearly point out' how the reagents acyl chlorides, the anhydrides, or any suitable We. have discovered that if various oils or fats or their-functional equivalents of the kind prejyiously described are reacted with hydroxy Qt'ertiary amines, one obtains materials of the kind characterized by the fact that. the fatty acid radicals are present in the amine compound in 'an esterifled. form.

As to the production of amines employed in the products are well known compositions of matter and that the methods of producing the same are well known and do not require further elaboration, with the exception that the produc-' tion of the materials from hydroxylated fatty acids, that is, ricinoleic acid, hydroxystearic acid, and the like, appears to yield different products dependent upon whether or not the ester is used on one hand or the fatty acid, for example, is used on the other. The reason for this different state of affairs in regard to the hydroxy fatty acids is that an attempt to produce the products from the fatty acids results in polymerization, 'which is not true when the esters are employed. It is furthermore believed that the production of thesematerials in absence of the amine salts 1 acid, or functional equivalent.

taking place in varying proportions with the glycwax will be considered as a glyceride and indicated thus: (R.C OO) 3C3H5 Purely as a matter of convenience, triethanolamine will be selected as the tertiary hydroxyamine for reaction with the selected oil, fat, fatty The reactions eride may be indicated in the following manner:

sodium oleate, sodium carbonate, caustic soda,

-etc., may be present in amounts of about one-half of 1% or less. It is noted that the fatty acids are I employed in this instance'in the form of an ester,

, takeplace to any appreciable extent if the fatty acid-has been converted intothe soap or salt. Such salts are not functional equivalents.

It is to be remembered that the reactions take place in any event under conditions which are substantially anhydrous. In other words, if water is formed in an esterification reaction, such as one involving one mole of stearic acid, and one mole of triethanolamine, it isdriven oil or eliminated immediately because the temperature of reaction is above the boiling point of water. Naturally under such circumstances there 'is no objection to passing a dry inert gas through the mixture to hasten esteriilcation.v

Four additional facts must be borne in mind in regard to these compounds. In the first place, these amines which are employedas demulsifying agents in the present process are not quaternary ammonium bases or salts thereof. The

expression quaternary ammonium is properly OH.C:H4N

once-1'4 2.000 010,111 R.coo.ciH (I) R.COO-CzHx+OH.CaHr-N-)3 OH.C:H4N+C;H|(OH);

.OH.CaH4N OH.C:H4'N' 11.000

OH.C:H4 R.COOCSHS 0110.114 R-COO.CIH4 11.000 [1 R000 +OH.C|H N)3R.C00.C;H -N+2CzH:(OH)| 011.0 011.0 acoo-mm OH 12.000

. 0H.C1H4N 1z.coo 011cm, 11.000011];

The manufacture of these compounds is rela- 4 tively simple. The selected fatty oil and the selected hydroxy tertiary amine are mixed in suitable proportions and heated at some point above 'theboiling point of water, for instance, C., and at a point below the decomposition point of the amine or the fatty oil, for instance, 0., for a suitable period of time, such as 2 to 8 hours. Mild agitation is employed. A catalyst such as pointed out that an amide formation involves a I product in which there is a direct linkage between exclude amines having little or no basicity such as the ordinary aromatic amines or any amine havingat least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demulsifying agents and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived. from aryl amines. They are derived solely from alkyl,

alicyclic, or aralkyl amines having at leastone hydroxyl group present. It is true that in' the aralkyl aminesthere is an aryl group present, but it is not directly attachedto the nitrogen atom as in the case of aryi amines. but in fact represents nothing more or less than a substituted alkylamine. For instance, we consider benzylamine as being the primary'amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost'any basicity in -the forms of the esterified amine and that they exhibit all the properties of a basic amine, that is, they combine with water to form a base presumably,

a substituted ammonium compound, but not a quaternary ammonium compound insofar that there isalways one unsubstituted hydrogen atom of the ammonium radical present. They combine with various acids to form salts. For example,'they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid,'to form salts, It is understood that the reference in the specification and appended claims to the amines includes the basicform and the acid salts as well as the amines themselves. The characteristic demulsifying properties are contributed by .the 'amine, and it is immaterial -whether they may be considered as being in any one of the three followiiig forms:

. .(ThN

. /H ('Da j on (TnNHx in which T represents the substituents of the amino hydrogen, radicals of the parent ammonia from which allamines are hypothetically derived ,and X simply represents the acid'radical of 'any' acid employed. In referring to the amines derived by reactions involving fatty ,oils and triethanolamine, it is to be noted that the products may .be characterized by the following formula:

(0110.32,)... in which m is '1, 2, or 3, m is 0, 1, or 2, with the proviso that m+m ='3,- and n denotes any small whole-number, preferably less. than 10, and in the case of triethanolamine, denotes the numher 2.

If instead of employing triethanolamine, ethyl diethanolamine, or a similar aminewere employed, then the resulting products would be indicated by thefoll'owing type formula:

in which m is 1 or 2, m'.is or 1, m is 1, with the proviso that m+mf+ m"=3;and n has the same significance as above.

In event. that diethylaminoethanol were employed, it is manifest that another variation of the above formula would appear. It is also posfollowing formula:

sible to obtain compounds from such materials as acetylated triethanolamine in whichthe acetyl radical has replaced one hydrogen atom of one of the hydroxy ethyl radicals. Acetic acid in this instance maybe considered typical of the lower fatty acids which have less than 7 carbon atoms.

If such monoacetylatedtriethanolamine were radical indicated by Cal-I21; maybe a radical such as a Cal-I4 radical, CBHG radical, Gil-ls radical, C5H1o radical, or it may be an alicyclic radical or an aralkyl radical, as will become obvious from the kind of amines subsequently enumerated. Furthermore, where the radical.CnH2n+1, which is a typical alkyl radical, appears, it may be a methyl radical, ethyl radical, propyl radical, butyl radical, amyl radical, hexyl-radical, octyl radical, etc. On the other hand, instead of being a monovalent alkyl radical, it may bea monovalent alicyclic radical such as a cyclohexyl' radical, or

it may be an aralkyl radical, such as a benzyl radical. In the claims appended hereto, it is understood that the expression alkylolhincludes the hydroxy hydrocarbon radicals whether derived'from alkyl, alicyclic, or aralkyl radicals. v It is furthermore understood in the hereto appended claims that the expression hydroxy alkyl"- includes hydroxy alicyclicas well as hydroxyaralkyl radicals, provided that in the latterthe hydroxyl group is attached to the aliphatic side chain. Attention is also directed to the fact that the teritray amines involving the glyceryl radical (CsH5OHMmay substitute for the hydroxy alkyl radicals of-the kind described. It is also understood that alkyl-oxy-alkyl radicals are the equiva lent of an ordinary alkyl radical, insofar that they might appear in products such as thetrihydroxy ethyl ether of tr-iethanolamine which may be indicated by the following formula:

' mczniocznioms See other examplesdescribed in U S. Patent No.

1,923,178, dated August 22, 1933, to Ulrich et' al.'

Such material would be the obvious functional equivalent of triethanolamine in reactions of the kind contemplated in the manufacture of the demulsifying agents employed in the present,

process. H

The amine employed as a demulsifying. agent in the present process might be indicated by the in which m-is 1,2, or 3,-m' is o, 1, or 2, with the proviso that m+m"=3, T is an alkyl radical or a radical of thejtype (R'COO.alkyl) or a hydroxy alkyl radical, and RLCOO represents an acid radical having less than 7 carbon atoms. The expression alkyl.is used in the bgg'ad sense previously specified, and it is also'it =',-be repeated that the amine may be in the midi of the base or in the form-of a salt.

Suitable bases which may be reacted with fatty oils or completely esterifled fatty oils or esterliied fatty acids to produce the demulsifying agent contemplated in the. present process include: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, dlethanol propylamine,

' etc.; tertiary glyceryl amines such as monOBIY- I C. for about 2 hours.

ceryl diethylamine', monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine, etc. Other examples include diethanol methylamine, tripropanolamine, dipropanol methylamine, cyclohexanol diethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolamine, dibenzylethanolamine.. benzyl dipropanolamine, tripentanolamine, trihexanolamine, ethyl hexyl ethanolamine, octadecyl diethanolamine, polyethanolamine, etc.

In indicating the various hydroxylated tertiary amines of the non-aryl type which may be employed to produce the amine contemplated as the demulsiiying agent oi the present process, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, it diethyl amino ethanol is treated with lactic acid so as to form lactyl ethanol diethylamine of the following formula:

0110,11. then such compound would be included due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Example I 'Castor oil (triricinolein) is employed. For sake of convenience, its molecular weight is considered as being 925. Commercial triethanolamine and castor oil in the proportion of one mole of castor oilto three moles of triethanolamine are heated to a temperature between 150' and 180 Mild agitation is employed. The reaction product so produced may be used as such or may be converted into the acetate by the addition of the maximum amount of glacial acetic acidwhich can be added without causing acidity to methyl orange indicator. Generally speaking, this will require about three moles of glacial acetic acid which can be added without causing acidity to methyl orange indicator.

7 Example II Triglycerylamine (tridihydroxy propylamine) is substituted for triethanolamine in Example I.

Example III Diamy'l monoglycerolamine (1-di-amyl amino propane 2,3, diol) is substituted for triethanola-' mine in Example I.

Example IV Dicyclo hexylamine is reacted with glycerol monochlorhydrin to give monoglyceryl dicyclohexylamine. This product is substituted for triethanolainine in Example 1.

Example V Dibenzylami'ne is reacted with glycerol -monochlorhydrin to produce monoglyceryl dibenzylamine. This product is substituted for triethanolamine in Example 1.

Ethyl hydroxy stearate is reacted in the previous\ manner with the various amines above enumerated in the various examples. In this case one mole of ethyl dihydroxy stearate is reacted with one mole'of the tertiary hydroxyamine. I

Example VIII Methyl hydroxy stearate is employed to replace ethyl dihydroxy stearate in the examples indicated under Example VII above.

We desire to emphasize that the products obtained in the above examples may be used in the form of the amine by direct contact with an emulsion without contact with water. They may be contacted with water, thatis, used in the form of a solution so as to produce in a greater or lesser degree the amine base. Furthermore, any of the products above described may be combined with suitable acid. Acetic acid may be employed- Hydrochloric acid is particularly desirable. In some instances, acids such as oleic acid or naphthenic acid may be 'employed to give a suitable salt.

In examining the method of manufacture of these compounds as previously described, it is apparent that certain by-products appear such as glycerine, monoor di-glycerides, etc. From a practical standpoint it is unnecessary to separate these cogeneric materials, though it would be possible to do so by conventional processes. It is quite possible thz these materials which appear as a part of the reaction mass contribute to a greater or lesser degree to the demulsifying power of the amine body. It may be that some of these materials which appear in the reaction mass cannot be completely identified as to their form. Eor instance, it is at once possible to see that condensation products might be formed under proper conditions between amines of the kind contemplated as demulsifying agents in the present process and either glycerol 01' triethanolamine, by virtue of anether linkage. In view of this fact, in the appended claims the demulsifying agent will not only be described in terms of the chemical structure of the amine, butalso in terms of the method of manufacture. The purpose of the claims, which are characterized by reference to the method of manufacture, is to specifically include the general reaction mass produced in the manufactured the amine bodies.

It is well known that fatty acids-can be modified by addition or substitution, so that the resultant products are still monobasic. I For .in- -stance, oleic acid can be converted into'oleic acid dichloride. Stearic acid can be converted into .dichlorstearic acid, etc. In these instances the modified fatty acid still acts as the functional equivalent of the fatty acid for purposes such as the reactions indicated in describing the manufacture of the demulsifyingagents used in the present invention. It is to benoted that the introduction of a chlorine atom, bromine atom, iodine atom, or an alkyl radical, for example, does not result in converting a monobasic acid,

i. e., the ordinary fatty acid, into a polybasicacid. It is not intended that functional modification shall include such derivatives as obtained by treating ricinoleic acid, for example, with sulfuric acid, phosphoric acid, boric acid, phthalic acid, .oxalic acid, maleic acid,etc., all of' which resultsin the introduction of a radical having an ionizable hydrogen atom; or in other words, converting the monobasic fatty acid into a polybasic acid, in which caseall the acid radicals may be carboxy in nature or they may be mixed in nature, i. e., both sulfo and carboxy.

One should not-lose sight of the fact, however, that the present invention is concerned particularly with the employment of certain chemical compounds of definitely stated composition which are present in significant or predominant amounts inthe mixtures obtained by the reactions described. Needless to say, the employ-- ment of the selected demulsifying agents in the art of breaking crude oil emulsions is not limited to any particular method of manufacture except in the appended claims, in which specific reference is made to manufacturing procedure.

Attention ,is directed to the fact that the word amidification" has been applied to the reaction involving the replacement of an amino hydrogen atom by. an acyl radical without conventional limitation to a reaction involving ammonia. The

replacement of the amino hydrogen atom of a primary amine or a secondary amine by an 'a'cyl radical has been considered as being amidifica such, or after dilution with any suitable solvent,

such as water, petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl VP alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may

be empl'oyedfas diluents. Miscellaneous solvents,

such as -pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petro- ,leu'm, etc.-, mayibe employed as diluents. Similarly, the material or materials employed as the de mulsifying agent of our process may be admixed with one' or more of the solvents customarily used in connection with conventional demulsify-.

ing agents. Moreover, said material or materials may be used alone or in admixture with other suitable well known classes of demusifying agents.

. It is well known that conventional demulslfylng agents may be used in awater -soluble form,

or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibitsrelatively 5 limited water solubility and relatively limited oil solubility. However, since 'such reagents are sometimes used in a ratio of V1 to 10,000 or 1, to 20,000, or even 1 to 30,000, such an apparent insolubility inoil and water is not significant, be- 1 cause said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

. We desire to point out that the superiority of the reagent or'demulsifying agentcontemplated in our process is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commerciahvalue, as it will economically break or resolve oil field emulsionsb in a number of cases which cannot betreat 1 demulsifying agents heretofore available,

In practicing our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways or by any' of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as so the electrical dehydration process.-

Having thus described our inventionjwhat we claim as new and desire to secure. by Letters Patent is:

1. A'process for breakingpetroleum emulsions at of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent compr sing a composition of matter derived by reacti n, under substantially anhydrous conditions, between a chemical compound containing an acyl radical derived from a fatty 1 acid and a non-aryl tertiary 'hydroxy amine within the molal ratio of 1:1 and 1:3, at a temperature above the boiling point of water and below the point of decompositiomjsaid reaction being conducted in a manner to yield a substan- A tial quantity of basic material in which the fatty acid radical is attached to the basic nitrogen atom through a'carbon atom chain;-'with the added .proviso thatin said basic material the ratio of said acid radical to-the amino nitrogen atomshall be at least 1:1 and not more than 3: 1; and said basic. material being further characterized by absence of amide and polyafminoradicals. V

2. A process for breaking petroleum emulsions of the 'water-in-oil type; characterized by subjecting the emulsion to the actionof ademulsifyl ing agentcomprising a composition of matter derived by reaction, under substantially a ydrous conditions,'between a fatty acid glyceri e and a non-aryl tertiary -hydroxy amine Within the molal ratio of 1:1 and 1:3, 'at a temperature above the boiling point of water, and below the point of-decomposition; said reaction being conducted in a manner to yield a substantial quantity of to d as easily or at so low a cost with the 30 basic material in which 'the fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain; with the added proviso that in said basic material the ratio of said acid radical to -the amino nitrogen atom shall be at least 1:1 andnot more than 3:1; and said basic material being further characterized by absence of amide and polyamino radicals,

-3. A process for breaking petroleum emulsions of the wate-r-in-oil type, characterized by subjecting the emulsionto the action of a demulsifying agent comprising a composition of matter derived by reaction, under substantially anhydrous conditions, between a fatty acid glyceride and triethanolamine, within the molal ratio of 111 and 123, at a temperature above the boiling point of water and below the point of decomposition; said reaction being conducted in a'manner to yield a substantial quantity of .basic materialin which the fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain; with the added proviso that in said basic material the ratio of said acid radical to the amino nitrogen atom shall be at least 1:1 and not more than 3:1; and said basic material being further characterized by absence of amide and polyamino radicals, I

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a chemical comp und of the type indicated by the formula:

in which m is, 1, 2, or a, m" is o, 1, or 2, with the proviso that m+m=3, T is selected from the class consisting of alkyl radicals, or radicals of the and R600 represents a fatty acid radical, and R'.COO is an acid radical having less than 7 carbon atoms.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsions to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

in which m is 1 or 2, and m is 1 or 2, with the proviso that m+m'=3, T is a hydroxy alkyl radical, and R000 is a fatty acid radical.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by, subjecting the emulsion to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

acoomk i in which 111 is 1, or 2, and m is-'1, or,2, with the proviso that m+m'=3, I is a hydroxy ethyl radical, and R000 is a fatty acid radical.

7. .A process for breaking-petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

in which m is '1 or 2, and m is 1 or 2, with the proviso that 1n+m'=3, T is a hydroxy ethyl radical, and R'.COO is a ricinoleic acid radical.

MELVIN DE GROOTE. IBERNHARD KEISER. CHARLES BLAIR, JR. 

